Low bulk density sodium polyphosphates

ABSTRACT

Sodium polyphosphates and particularly sodium tripolyphosphates which generally find use as detergent builders are prepared in low bulk density, high relatively non-frangible granular yields by spray drying an aqueous solution of monosodium/disodium orthophosphate salts having an NaO:P2O5 ratio of from 1 to 2, hydrating the spray dried product or the fines to a LOI of between about 18% and about 25% and intermolecularly dehydrating the hydrated product in a fluidized converter at a temperature of between about 200* C. and 500* C. to provide the desired product.

llnited States Patent fiyer et al. 1 Mar. 21, R972 [54 LOW BULK DENSITY SODIU 3,382,036 5/1968 Post et al. ..23/l06 POLYPHOSPHATES [72] inventors: James N. Dyer; Leo B. Post, both of New f EmmlrilerEarl Thomas Cit when J Rose Yonkers a of Assistant Exammer-Gregory A. Heller Attorney-Robert C. Sullivan, Wayne C. Jaeschke, Daniel S. Ortiz and Paul J .luettner [73] Assignee: Stauffer Chemical Company, New York,

N.Y. [57] ABSTRACT Filedi l 1969 Sodium polyphosphates and particularly sodium [211 App! No; 857,393 tripolyphosphates which generally find use as detergent builders are prepared in low bulk density, high relatively nonfrangible granular yields by spray drying an aqueous solution [52] US. Cl ..23/107, 23/106 of monosodium/disodium orthophosphate salts having an [5]] iff C0lb25/30C0lb25/38 NaO:P O ratio of from 1 to 2, hydrating the spray dried leld of Searc A, product or the s to a of between about and about 25% and intermolecularly dehydrating the hydrated product [56] References Cited in a fluidized converter at a temperature of between about UNITED STATES PATENTS 200 C. and 500 C. to provide the desired product.

3,233,967 2/1966 Shen ....23/l06 4 Claims, 1 Drawing Figure Liquid Feed Mixture PRODUCT Patented March 21, 1972 Dust Re cycle Cyclone Fines Course Particles MIXER LOW DENSITY s s m PRODUCT FLUIDIZED BED LOW BULK DENSITY SODIUM POLYPHOSPHATES BACKGROUND OF THE INVENTION The present invention relates to a process for preparing lowdensity sodium polyphosphates in a fluidized bed from a conditioned feed mixture of sodium orthophosphates which has been processed to furnish a low bulk density product upon molecular or intermolecular dehydration. In particular, the present invention relates to a process for preparing sodium polyphosphates in at least 90% granular product form from a fluidized bed reactor.

Numerous sodium phosphates, e.g., sodium tripolyphosphates, are available commercially, each tailored to suit at least one particular domestic or industrial use. These products are prepared by converting mixtures of phosphate salts at elevated temperatures to the desired product as illustrated by the following reaction scheme for preparing sodium tripolyphosphate:

300 C. 2NaaHPO4 NaHaPOi NaiPaw 21120 The reaction proceeds well at temperatures above 300 C. though temperatures as low as 200 C. and as high as 500 C. can be used. The two reactants (Na-,HPO, and NaI-I PO or ortho salts are generally prepared by admixing sodium carbonate with phosphoric acid in an aqueous medium. Close control is required during this reaction to insure an almost exact 2:1 ratio of dicmono sodium ortho phosphate salt. Variations in the ratio of di:mono sodium ortho phosphate lead to the formation of sodium pyrophosphateand sodium metaphosphate. Unreacted sodium carbonate can cause formation of further impurities. The purity and close intermingling of the ortho salts at the time conversion to the sodium phosphates is necessary to provide the desired final product. The proper preparation of the reaction feed mixture is essential to providing a proper final product. 1

In addition to the chemical product itself, care is also given to the final physical form of the product. There are commercially available today sodium phosphates in a number of densities, each tailored to suit a particular use or uses. The so-called light density" sodium tripolyphosphates which are commercially available (usually 25 to 40 pounds per cubic foot) find major application as detergent builders where a fast rate of solution is desired; or to provide a porous absorptive particle as a carrier for other ingredients such as enzymes, surface active agents and the like; or to provide bulk to aproduct; or in certain types of detergent tablets. The density of any condensed sodium phosphate is normally fixed within limits of the process selected for its preparation. The light density" sodiurn tripolyphosphates are often produced by flash drying, a liquid feed, e.g., in spray drying equipment and conducting the spray dried material into a calciner for conversion into the sodium tripolyphosphate. Several difficulties have arisen with this process. The dried product from the spray drier is characterized by an extremely wide range of particle sizes ranging from dust to coarse particles. The calciner is limited in its ability to agglomerate or in any way assist in reducing the amount of small particles in the final product. The small particles or fines and dust must be separated and either recycled or sold as a separate powder product. Due to present market conditions, an economical process requires the use of the fines and dust. The market for this powdered product has dwindled extensively in the past few years so that the fines and dust of the process are extremely undesirable. Workers in the prior art have attempted to overcome this problem by the process outlined in the US Pat. No. of Post et al., 3,382,036, issued May 7, 1968. In this process, a dry, crystalline feed mixture of orthophosphate salts is introduced into a dehydrator to remove the water of hydration from the salts. The product of the dehydrator is milled, rehydrated, remilled to a preferred loss on ignition (LOI) of between about 14% to about 18%, and then introduced into a fluidized bed in order to provide a low density sodium tripolyphosphate product. In the process using regular milled salts from well defined crystals of mono and disodium phosphate, agglomeration proceeds along with conversion in the fluidized bed reactor. Water from the crystals is released slowly causing a tacky condition to exist for several minutes. The release of water in the conversion induces a tacky stage which allows the feed particles to adhere to the tripoly phosphate particles in the fluid bed and in this manner produces a coarse granular product. However, the

desirability of this process is reduced by the requirement of the numerous milling steps. Also, the product of the Post et al. patent is highly frangible, tending to break down during transportation due to the rubbing of the particles together or with the walls of the transport means. This tends to produce fines which are undesirable in some areas of use. It has now been found that these disadvantages can be overcome.

THE INVENTION In accordance with the present invention, there is provided a process for producing low density sodium phosphates in an increased yield of granular product comprising, converting at a temperature of between about 200 C. and about 500 C., a conditioned feed of ortho phosphate salts, said conditioned feed being prepared by spray drying an aqueous solution of orthophosphate salts selected from the group consisting of monosodium phosphate, monohydrate, and disodium phosphate, duohydrate, having an Na O:P- O ratio of from 1:2 inclusive, hydrating the spray dried feed with water to a loss on ignition or LOI of between about 18% and 25% by weight to provide the conditioned feed. The product of the invention provides strong granular particles which are not as frangible as products prepared from prior art methods. In a preferred form of the invention, the condition feed is prepared by taking the spray dried feed of orthophosphate salts and separating out a substantial portion of the fine particles of the spray dried product, hydrating the fine particles with water to an LOI of between about 18% to about 25% by weight and recombining the hydrated spray dried particles with the coarse spray dried particles to provide the conditioned feed. After conditioning,

the feed is preferably fed to a fluidized bed for conversion into the sodium polyphosphate in the manner prescribed in the prior art.

Although the present process is not dependent upon theoretical considerations for operability, it is believed that hydration of the spray dried orthophosphate feed salts causes an agglomeration of the fine particles in the hydration stage. In the fluid bed, the spray dried particles convert rapidly and the water from these particles evaporates quickly. Tackiness is brief due to porosity of these particles and the small cluster of crystals that form through rapid instantaneous evaporation. Spray dried particles are spherical and provide a minimum of surface area whereas other particles such as the milled salt provides a greater surface area to allow greater contact with one another. Spray dried particles tend to pass through the fluidized bed converter with little change in particle size. The present invention is based on the finding that by hydration of the spray dried ortho salts prior to conversion, agglomeration is markedly improved apparently by providing water of hydration as a means of dissolving mono and di sodium phosphate and creating a slower release of water during the conversion.

DESCRIPTION OF DRAWING Referring now to the drawing, there is set forth a preferred process for producing sodium tripolyphosphate (hereinafter alternatively STPP). The present invention will be illustrated with regard to the preparation of STPP although not necessarily limited thereto.

In the drawing there is shown a spray drier to which is fed a liquid feed mixture of orthophosphate salts having the approximate mixture of two parts disodium phosphate for eachone part monosodium phosphate by weight. Any type of standard spray drying equipment can be utilizedlhough large diameter spray driers are preferred. The spray drie'r can use either the rotating disc atomizer or the spray nozzle atomizer, though the former is preferred. The liquid feed mixture can contain any concentration of the ortho salts though it is preferred that the solution be as concentrated as possible so that a limited amount of water has to be removed in the spray drying operation. Upper limits on concentration are dictated by the ability of the solution to pass through the nozzle of the spray drier, or be effectively atomized by the rotary disc. Practical solids concentration for drying efficiency are preferably maintained within the range of from about 40% to about 65%, though it is more preferred to maintain the solids content within the range of from about 45% to about 55%. The spray drier is operated at drying or inlet temperatures of from about 150 C. and 500 C. though preferably at temperatures of between 350 C. and 450 C. The spray drier is operated at outlet temperatures of from about 110 C. to about 250 C. and preferably from about 130 C. to about 160 C. More preferably, the outlet temperature is maintained between about 145 C. and about 160 C. Surface temperatures of the product of above about 175 C. are to be avoided inasmuch as anhydrous monosodium phosphate and disodium phosphate are molecularly dehydrated to form, respectively, sodium acid pyrophosphate and tetrasodium pyrophosphate or intramolecularly dehydrated to form sodium tripolyphosphate. The formation of appreciable amounts of these condensed phosphates during the preparation ofthe feed, (e.g., over to by weight of the total feed) is normally undesirable since they can prevent proper agglomeration of the feed in the later conversion step. Thus, outlet temperatures of above about 175 C. are generally to be avoided. Outlet temperatures can be increased if the residence time of the particles is reduced so that the surface temperature of the particles does not substantially exceed about 175 C.

Following spray drying, the chamber" product, e.g., the coarse particles which collect at the bottom of the spray driers, is separated from the fines. The coarse particles are conducted directly to the fluidized bed converter for conversion into sodium tripolyphosphate. Fines which are still airborne in the outlet gas stream are conducted to a cyclone where the fine particles are separated from the gas stream. Any entrained particles are sent through a scrubber for recycle. The tines which generally comprise a particle size of from 0 to about 150 microns are then conducted into an hydration apparatus for increasing the LOI to an amount of between about 18% to about The type of apparatus which can be used for hydration can by any unit which provides for mild agitation during the addition of the water to the spray dried fines. A preferred apparatus consists of rotary drum drier equipped with water sprays and lifter vanes. Such an apparatus aids in the uniformity of hydration and providing continuous operation. To prevent condensation on the hydrator roof and walls it is usually desirable to provide means for drawing fresh air across the agitated bed. It is preferable that the temperature of the mixture to the hydrator be maintained below about 50 C. When a higher temperature is used the mixture may become tacky and difficult to handle during later operations. Inasmuch as it is desired to have a high LOl and a high porosity product, the cooling ofthe feed before hydration is advantageous.

In order to effectively agglomerate the cyclone-separated spray dried particles, the L01 of the particles must be increased to at least 18% in the hydrator. Hydrating the product to over 25% L01 provides a feed which tends to be wet and difficult to handle. Porosity can also be lost by the liquiflcation ofthe orthophosphates.

The conditioned feed is then passed directly into the fluidized bed for conversion at a point either above or below the upper level of the bed. In the fluidized bed the temperature is maintained at a temperature between about 200 C. and 500 C. to effect conversion (i.e., molecular or intermolecular dehydration). Dombroveskii, N.M., Russian .lournal of Inorganic Chemistry, January, 1962, pp. 47-51. The particles are generally converted with little change in size during the fluid bed reaction. Where desirable, the fluidized bed converter can be replaced with other types of heating apparatus, such as rotary kilns. The fluidized bed is preferred to other types of apparatus for the manufacture of low density STPP.

The invention will be further illustrated in the Example which follows.

EXAMPLE 1.

An aqueous solution of mono sodium phosphate and di sodium phosphate was prepared by reacting soda ash and 87% l-l PQ in the stoichiometric quantities necessary to provide a reaction mixture having an Na,O:P O: ratio of between 1.66 and 1.70. Water was added to maintain a 50% solids concentration. This solution was then dried in a 26 ft. diameter spray drier using a rotary disc atomizer. The inlet air temperature was about 350 C. and the outlet air temperature was about 150C. The dried solids (ortho salts) were then screened through an -mesh screen resulting in 20,000 lbs. of plus 80 mesh solids and 20,000 lbs. of through 80-mesh material. The through 80-mesh solids were then sent through a 4 ft. diameter X 20 ft. long rotary drum where 15% water was added to the solids. The moistened ortho salts now having an L01 of 23% were then mixed with the dry solids to form a total of 40,000 lbs. of feed salts. The feed salts were then converted to sodium tripoly phosphate at a rate of 3,860 lbs/hr. of ortho salts in a 9.5 ft. diameter fluid bed reactor. The reactor temperature was 320 C. This resulted in a yield ofproduct with a bulk density of 31.3 lbs/cu. ft. and a particle size distribution between 14 and 80 mesh.

Another run using spray dried salts prepared in the same drier and converted in the same reactor at the same operating conditions but without the hydration step was performed. The test lasted 32 hours but yielded only 40% of 29-31 lb./cu. ft. product. The balance of the feed salts ended up as sodium tripoly phosphate fines which accumulated in the reactor and had to be removed in order to make room for fresh feed.

The present process may be advantageously used to produce sodium phosphates having bulk densities below about 55 lbs./cu. ft. The preferred bulk density is between 25 and 35 lbs./cu. ft. From a practical standpoint, and in part due to particle frangibility, 20 lbs/cu. ft. appears to be about the lowest bulk density possible on a continuous commercial scale. The medium bulk density phosphates, e.g., those above about 40 lbs/cu. ft., may be useful in applications where it is necessary for the particles to absorb quantities ofliquids, e.g., detergent mixtures, etc. Due to the greater porosity of the sodium phosphates produced from spray dried feed they tend to have greater capacity for absorbing and retaining liquids. Lower density sodium phosphates have an even greater porosity and capacity for holding such liquids, and consequently are highly preferable for use in detergent tablets and the like. As indicated hereinbefore, the porosity (bulk density) of the sodium phosphate produced by the process of the invention is controlled by the conditioning procedure used for the feed. Thus, controlled spray drying along with multiple screenings of the spray dried materials could be used to furnish very low density products.

The sodium phosphates which may be produced by the present process are those having Na O:P O ratios between 1 and 2, including monosodium phosphate, sodium tripolyphosphate, and tetrasodium pyrophosphate. Further, any mixtures of two or more of the sodium phosphates, e.g., tetrasodium pyrophosphate and sodium tripolyphosphate, are within the scope ofthe invention. it should be noted that many of the commercially available condensed phosphates may include small amounts, up to about 10-15% by weight, of other phosphates. For instance, the usual commercial STPP will normally contain about 110% by weight of sodium metaphosphate, sodium pyrophosphate and sodium orthophosphates. Selection of the proper proportions of mono-and disodium orthophosphates to serve as feed to produce any of the sodium phosphates or mixtures thereof will be obvious to those skilled in the art since the product will have the same Na O:P O,, ratio as the feed. For example, it will be obvious to use two moles of disodium orthophosphate (ratio 2.0) for every mole of tetrasodium pyrophosphate which is to be produced. Also, where a mixture of condensed phosphates is to be produced, a mixture of mono-and disodium orthophosphates having the same Na O:l=' O ratio will provide the desired feed.

it is also important to note that sodium tripolyphosphate, which represents a preferred product of the present process, has two known crystalline modifications, the so-called high temperature form, commonly denoted Form I, and the low temperature form, commonly denoted Form ll. Under atmospheric pressure, these polymorphic forms are reported to be enantiotropic with a transition temperature at 400-470 C. By the present process, each form, or mixtures thereof, may be produced.

What is claimed is:

l. A process for producing low density sodium polyphosphates which comprises intermolecularly dehydrating at a temperature within the range of 200 C. to 500 C. a conditioned feed prepared by spray drying an aqueous solution of orthophosphate salts selected from the group consisting of monosodium phosphate, monohydrate disodium phosphate duohydrate and mixtures thereof having an Na ozP q ratio offrorn l to2 inclusive; said spray drier having an inlet temperature in the range of from about C. to about 500 C. and an outlet temperature maintained within t range of between about 130 C. and about C., and the surface temperature of the spray dried product not exceeding about C., separating the fine particles of the spray dried product having a particle size of less than 150 microns from the coarse particles; hydrating the fine particles with water to a loss on ignition from about 18% to about 25%; and recombining the hydrated spray dried fine particles with the coarse particles to provide said conditioned feed.

2. A process as recited in claim 1 wherein said Na O:P O ratio is about 1.67.

3. A process as recited in claim 1 wherein said conditioned feed is intermolecularly dehydrated by continuously feeding said conditioned feed to a dense fluidized bed of sodium tripolyphosphate maintained at a temperature of between about 200 C. and 500 C. while continuously withdrawing product from said fluidized bed at a substantially equivalent rate.

4. A process as recited in claim 1 wherein said spray dried product is hydrated to a loss on ignition of from about 21% to about 23%. 

1. A process for producing low density sodium polyphosphates which comprises intermolecularly dehydrating at a temperature within the range of 200* C. to 500* C. a conditioned feed prepared by spray drying an aqueous solution of orthophosphate salts selected from the group consisting of monosodium phosphate, monohydrate disodium phosphate duohydrate and mixtures thereof having an Na2O:P2O5 ratio of from 1 to 2 inclusive; said spray drier having an inlet temperature in the range of from about 150* C. to about 500* C. and an outlet temperature maintained within t range of between about 130* C. and about 160* C., and the surface temperature of the spray dried product not exceeding about 175* C., separating the fine particles of the spray dried product having a particle size of less than 150 microns from the coarse particles; hydrating the fine particles with water to a loss on ignition from about 18% to about 25%; and recombining the hydrated spray dried fine particles with the coarse particles to provide said conditioned feed.
 2. A process as recited in claim 1 wherein said Na2O:P2O5 ratio is about 1.67.
 3. A process as recited in claim 1 wherein said conditioned feed is intermolecularly dehydrated by continuously feeding said conditioned feed to a dense fluidized bed of sodium tripolyphosphate maintained at a temperature of between about 200* C. and 500* C. while continuously withdrawing product from said fluidized bed at a substantially equivalent rate.
 4. A process as recited in claim 1 wherein said spray dried product is hydrated to a loss on ignition of from about 21% to about 23%. 